Emulsifying and textile softening phosphonium compounds, process for preparing the same and other compounds, reactive intermediates

ABSTRACT

NOVEL PHOSPHONIUM COMPOUNDS AND PROCESSES FOR THEIR PREPARATION ARE DISCLOSED. THESE NOVEL PHOSPHONIUM COMPOUNDS ARE USEFUL AS TEXTILE SOFTENING AGENTS, EMULSIFYING AGENTS AND ANTI-BACTERIAL AGENTS.

United States Patent EMULSIFYING AND TEXTILE SOFTENING PHos-' PHONIIHVICOMPOUNDS, PROCESS FOR PRE.

PARING THE SAME AND OTHER COMPOUNDS REACTIVE INTERMEDIATES TerenceWilliam Rave, Wilmington, Del., assignor to The Procter & GambleCompany, Cincinnati, Ohio, a corporation of Ohio No Drawing. Originalapplication Dec. 30, 1965, Ser. No. 517,826, now Patent No. 3,475,490.Divided and this application Aug. 21, 1968, Ser. No. 754,478

Int. Cl. B01f 17/16; Clld 3/066; D06m U.S. Cl. 252-8.8 11 ClaimsABSTRACT OF THE DISCLOSURE Novel phosphonium compounds and processes fortheir preparation are disclosed. These novel phosphonium compounds areuseful as textile softening agents, emulsifying agents andanti-bacterial agents.

3,553,129 Patented Jan. 5, 1971 These and other objects will be apparentfrom the description of the invention which follows.

According to this invention, it has been found thatphosphiniminophosphonium salts having the following structural formulaare effective'and durable textile softening agents and effectiveemulsifying agents:

ea R RRPLLNLP RJRR5 wherein R is an aliphatic radical containing from 1to about 18 carbon atoms; R R R and R are aliphatic radicals containingfrom 1 to about 4 carbon atoms; R is an aliphatic radical containingfrom about 12 to about 18 carbon atoms; and X is an anion which permitsadequate solubility and hydrolytic stability of the salt.

The term "phosphiniminophosphonium is used herein to denote a compoundcontaining a [EP;N;;PE1

linkage, which linkage is explained hereinafter. Compoundscontaining'this linkage have been described in the prior art. However,compounds containing this linkage which are effective textile softeningagents and elfec tive emulsifying agents are not known to have been sodescribed.

There are several textile softening agents which are presently known tobe commercially available which are of much different chemical structurefrom the compounds j of the present invention. Some of these softeningagnts while eifectively softening textiles thereby reducing oreliminating harsh feel, do not resist removal. In other words, if thesoftened textile is washed without reapplicar tion of softening agent,the previously applied softening agent is removed by the washing fromthe textile, and harsh feel is again present. A durable softening agent,that is a softening agent which resists removal even after severalwashings of the textile, is advantageous to the consumer in that thenecessity of continual reapplication of softening agent is eliminated.

It is, therefore, an object of this invention to provide novelphosphiniminophosphonium salts which are effective ing agents.

It is a' further object of this invention to preparephosphiniminophosphonium salts by heating aminophosphonium salts.

It is a further object of this invention to prepare phos- .60 anddurable textile softening agents and effectiveemulsifyphiniminophosphonium salts by reacting N-alkali-metal phosphinimineswith trisubstituted phosphine dihalides or can be employed Thisstructural formula and more particularly thelinkage in this structuralformula is a resonance structure. Thus, this structural formularepresents the following structural formulas which are in resonance andin which R, R R R R, R and X are defined as above:

The salts defined by this structural formula can be symmetrical orunsymmetrical. R, R R R and R can each be of different chain lengthswithin the same compound. The aliphatic radicals in this structuralformula can be saturated or unsaturated and branched or straight chain.For example, these aliphatic radicals can be alkyl, substituted alkyl,alkenyl and substituted alkenyl radicals. The term alkyl is used hereinto include only saturated carbon chains. The term alkenyl. is usedhereinto include carbon chains containing one or more double bonds.

The exact nature of the anionic portion of the abovephosphiniminophosphonium salts is thought to be immaterial .so far asthe textile softening and emulsifying properties of these new compoundsare concerned. Accordingly, virtually any organic or inorganic anionwhich permits adequate solubility of the phosphiniminophosphonium saltsand which permits hydrolytic stability of of the salts, that is, whichprovides stable anionic and cationic moieties upon solution in water,may be found suitable depending upon availability and cost factors.

Thus, X in the above structural formula can suitably be, for example, ahalide, such as chloride, bromide, iodide 0r fluoride; a pseudohalide,such as cyanide, azide or thiocyanate; a sulfonate such as methanesulfonate or ptoluene sulfonate; a sulfinate, such as methane sulfinate;a fiuoroborate; sulfate, sulfite, nitrate, nitrite, phosphate, borate,methosulfate, chlorate, 'bisulfate, bisulfite, acetate,hexachloroantimonate and other anions.

Preferably, the aliphatic radicals in the presentphosphiniminophosphonium salts are alkyl radicals and the anion, X, isselected from the group consisting of halides and pseudohalides.Symmetrical phosphiniminophosphonium salts of the present invention areespecially preferred for textile softening agents.

Emulsifying and textile softening phosphiniminophosphonium salts, noneof which are known to be described in theprior art and exemplary ofthose within the present invention are set forth in Table I belowwherein R, R R R R R5 and X are applied in the structural formula setforth above.

TABLE I R 1 R R R R X ethyl Methyl Methyl Tridecyl SOr do- Propyl. do BrMethyl do 01- do do I- Methy do do 01- EthyL. EthyL. Ethyl-.. CHaCOO- EMethyl Methyl Ethylene do 3- Methyl do ..do hyl Tetradecyl. Cl-ChloromethyL.-. do .do do.. do 3- do do d CN- Butyl Butyl HSOr MetgyMetly 8%- Oetadec l "do.-. 0.. Do. 3-hydroxypropenyl do do. Hexadecyl ClOleyl Methyl ..d0 d0 .d0 Oleyl Cl- *Where the valence of the anion isgreater than 1, a number of cations equal to this valence are present ineach salt molecule.

As previously stated, the above-described phosphiniminophosphonium saltsare especially useful as emulsifying agents. These salts ordinarily canbe used to produce oil-in-water emulsions that are stable for more thanone hour, the weight ratio of emulsifier to oil phase generally rangingfrom about 1:1000 to about 3:1. For example, these salts provide stablewater emulsions of dry cleaning solvents, such as tetrachloroethylene,and of other organic solvents, such as carbn tetrachloride. Moreover,these salts provide stable water emulsions of glyceride oils, such ascottonseed oil or soybean oil. In the preparation of such emulsions thephosphiniminophosphonium salt is preferably first dispersed in the oilphase to be emulsified, and the oil-emulsifier combination is then mixedwith the water phase. This is because these phosphiniminophosphoniumsalts tend to cause the formation of viscous solutions or gels whenadded by themselves to the water phase thereby making it difiicult toemulsify oil phase which is added to the water phase thereafter.

Morcver, these phosphiniminophosphonium salts are especially useful astextile softening agents. First of all, they effectively softentextiles, for example, towels, thereby reducing or eliminating harshfeel. Moreover, they are durable softening agents and after applicationto textiles resist removal and provide softening effect even after fiveto ten washings of such textiles. Thus, these salts are suitably used asactive ingredients in textile softener compositions, as softening agentsin industrial textile treatment where durable softening effect isdesirable or necessary, and as additives to detergent compositions.

The textile softener compositions referred to above can be in the formof liquids, granular products, tablets, and in other forms.

For example, a liquid textile softener composition can comprise fromabout 1% to about 15 by weight phosphiniminophosphonium salt and fromabout 85% to about 99% water. Such compositions also contain preferablyfrom about 1% to about 50%, and more preferably from about 1% to about10%, by weight of an alcohol containing from 1 to about 4 carbon atoms,such as, for example, ethanol or isopropanol, in place of an equalweight of water. This alcoholic component reduces the viscosity of thesoftener composition thereby causing it to be more readily pourable andalso reduces the tendency of the composition to become a gel. Thisalcoholic ingredient also desirably acts as a freeze point depressantthereby reducing the possibility of the composition freezing duringshipping whereby the compositions container is possibly ruptured. Thus,a preferred liquid textile softener composition herein consistsessentially by weight of from about 1% to about%phosphiniminophosphonium salt, from about 1% to about 50% alcohol, andfrom about 35% to about 98% water while an especially preferred liquidtextile softener composition herein consists essentially by weight offrom about 1% to about 15% phosphiniminophosphonium salt, from about 1%to about 10% alcohol and from about 75% to about 98% water. Optionalingredients for the present liquid textile softener compositionsinclude, for example, perfume, coloring agent, and up to about 1% ormore of a nonionic detergent such as, for example, nonyl phenoxypolyoxyethylene ethanol, containing 5 to 25 moles of ethylene oxide permole of phenol, to help stabilize the composition.

A granular textile softener composition can be prepared simply by mixingurea with the present phosphiniminophosphonium salts. These compositionscan comprise, for example, from about 5% to about 50%phosphiniminophosphonium salt and from about 5 0% to about urea.

These granular compositions can be compressed into tablets.

These softener compositions are applied, for example, by the housewifeto textiles during laundering. The housewife can cause the applicationof such a softener composition simply by adding it, for example, bypouring, into the rinse water which is present during the rinse cycle ofwashing machine operation. For effective and durable softening thetextile softener composition is added to the rinse water in amountsufficient to provide a concentration of phosphiniminophosphonium saltin the rinse water ranging from about 10 p.p.m. to about 500 p.p.m. andpreferably from about 25 p.p.m. to about 100 p.p.m.

Turning now to industrial applications, the presentphosphiniminophosphonium salts are advantageously employed in manyindustrial textile treating operations where durable softening effect isdesired. For example, the above 7 described textile softener compositioncan be applied to yard goods by passing such yard goods through a padcontaining this composition. Or yard goods can be treated with thepresent phosphiniminophosphonium salts at the same time they are treatedwith wash wear resins, for example, cyclic ethylene urea, to providesofter feel since treatment with wash wear resins alone usually producestextiles having harsh feel.

As explained above, these phosphiniminophosphonium salts can be employedas durable softening agent-additives to various detergent compositions,and ordinarily comprise from about 1% to about 15% by weight of suchdetergent compositions. The detergent active in these detergentcompositions is any detergent which is compatible with thephosphiniminophosphonium salt additive. This detergent active ispreferably a nonionic synthetic detergent or a zwitterionic syntheticdetergent since the phosphiniminophosphonium salt being cationic iscompatible with these detergents while such salt may not be compatiblewith soap and with anionic synthetic detergents. Thephosphiniminophosphonium salt additive can also be used in combinationwith cationic detergents or with ampholytic or amphoteric detergentswith the pH of the system adjusted so that such detergents are ca tionicdetergents. The detergent active ordinarily comprises from about 5% toabout 95% by weight of these detergent compositions.

with an organic hydrophobic compound, which may be aliphatic or alkylaromatic in nature. The length of the hydrophilic or polyoxyalkyleneradical which is condensed with any particular hydrophobic group can bereadily adjusted to yield a water-soluble compound having the desireddegree of balance between hydrophilic and hydrophobic elements.

For example, a well-known class of nonionic synthetic detergents is madeavailable on the market under the trade name Pluronic. These compoundsare formed by condensing ethylene oxide with a hydrophobic base formedby the condensation of propylene oxidewith propylene glycol. Thehydrophobic portion of the molecule, which, of course, exhibits waterinsolubility, has a molecular weight of about 1500 to 1800. The additionof polyoxyethylene radicals'to this hydrophobic portion tends toincrease the water solubility of the molecule as a whole and the liquidcharacter of the products is retained up to the point wherepolyoxyethylene content is about 50% of the total weight of thecondensation product. Other suitable nonionic synthetic detergentsinclude:

(1) The polyethylene oxide condensates "of alkyl phenols, e.g., thecondensation products of alkyl phenols The above mentioned nonionicsynthetic detergents may be broadly defined as compounds produced by thecondensation of alkylene oxide groups(hydrophilic in nature) having analkyl radical containing from about: 6 to 12..

carbon atoms in either straight chain or branched chain configuration,with ethylene-oxide, the said ethylene oxide being present in"amounts'e'qu'al to 5 to 25 moles of ethylene oxide .per mole of alkylphenol. The' alkyl substituent in such compounds may be' derived froinpolymerized propylene, 'diisobutylene, octane, or nonane, for

example. p 7 v v (2) Those derivedfrom the condensation ofethylene oxidewith the product resulting from the reaction' of propylene oxide andethylene diamin-produtits whichmay be varied in compositiondependingupon balance between the hydrophobic and hydrophilic elementswhich is desired. For example, compounds containing from about.-to'about 80% polyoxyethylene by weight-and having I a molecularstructure of about 5 000 to about l1,000 resulting from the-reaction ofethylene oxide groups with a. hydrophobic base, constituted ofvthereactionproduct of a coconut alcohol ethylene oxide';condensate havingfrom A l(+) R NR"Z wherein R contains from about 10 to about 18 carbonatoms and from about 0 to about 5 ether linkages, wherein R and R areeach selected from the group consisting of alkyl groups containing from1 to about 3 carbon atoms, wherein R is selected from the groupconsisting of alkylene and hydroxy substituted alkylene groupscontaining from 1 to about 4 carbon atoms, and wherein Z 'is selectedfrom the group consisting of groups. Specific examples of such compoundsare 1- (hexadecyldimethyla-mmonio)propane 3 sulfonate, 1- I(dodecyldimethylammonio)butane 3 sulfonate, and 1-(dodecyldimethylammonio) acetate. Some other common examples 01f thesedetergents are described in US. Pats. 2,082,275; 2,129,264, 2,217,846;2,255,082, 2,702,279.

The ampholytic and amphoteric detergents mentioned above arerepresented' by detergents such as dodecylbetaalanine, N-alkyltaurinessuch as the one prepared by reacting dodecylamine with sodiumisethionate according to the teaching of US. 2,658,072, N-higher'alkylaspartic' acids such as those producedaccording to the teaching ofUS. 2,438,091, and the products sold under the trade I name Miranol anddescribed in US. Pat. 2,528,378.

The detergent compositions herein contain from about 0% w 90%,preferably from 10% to 90%, by weight product of aliphatic alcohols 10to 30 moles of ethylene oxide per mole of coconut,- alcohol, the coconutalcohol fraction-having from 10 to 14 carbon atoms. i I v (4) Trialkylamine oxides and trialkyl phosphine oxides wherein one alkyl'radicalcontains from about 10 to about 18 carbon atoms, from 0 to about'5 etherlinkages, and from 0 to about 2 hydroxy groups'and. wherein the othertwo alkyl radicals each contain from lfto about 3 carbon atoms, from 0to about Zether linkages, and from 0 to about 2 hydroxy groups. Specificexamples are dodecyl diethanol amine oxide and tetradecyl dimethylphosphine oxide.

(5) Dialkyl sulfoxide detergents having the formula wherein R is ahydrocarbon group containing from about 10 to about 20 carbon atoms,from 0' to igbout 5 ofwater-soluble alkaline detergency builder salts,either of the organic'or inorganic types, and should provide a about0.7:1 to about 9:1. Examples of suitable watersoluble inorganic alkalinedetergency builder salts m alkali" metal carbonates, borates,phosphates, polyphos- -phat'es,-bicarbonates and silicates. Specificexamples of such. salts are sodium and potassium tetraborates, bicarbonates, carbonates, tripolyphosphates, pyrophosphates, orthophosphates,and hexametaphosphates. Examples of suitable organic alkaline detergencybuilder salts 'are:'

" (1) water-soluble aminopolycarboxylates (e.g., sodium a carbon chaincontaining no ether-linkagesand containing about 10 to 18 carbon" atoms,and"wherein'-R' -is'a short alkyl chain containing from about-"Itoabout-3 carbon atoms having 0-2 "hydroxyl groups attached "to andpotassium ethylenediaminetetraacetates, nitrilotriace-" tates, andN-(2-hydroxyethyl)nitrilo diacetates); (2)

waterasoluble salts of phytic acid (e.g., sodium and phytates- -see US.Pat. 2,739,942); (3) water-soluble salts of ethane 1hydroxyd,l-diphosphonate (e.g., the

trisodium. and tripotassium salts-see US. Pat. 3,159,-

581); 1(4) water-soluble salts of methylene diphosphonic acid (e.g.,trisodium and tripotassium methylene diphosphonate and the other saltsdescribed in the phonic acids (e.g., tr'isodium and tripotassiumethylidene,

isopropylidene, 'benzylmethylidene, and halomethylidene diphosphonatesand the other substituted methylene diphosphonates disclosed in thecopending application of Clarence H. Roy, Ser. No. 266,055, filed Mar.18, 1963 and now US. Pat. 3,422,021); (6) water-soluble salts ofpolycarboxylate polymers and copolymers as described in the copendingapplication of Francis L. Deihl, Ser. No. 269,359, filed Apr. 1, 1963and now US. Pat. 3,308,067. (Specifically, a polyelectrolyte buildermaterial comprising a water-soluble salt of a polymeric aliphaticpolycarboxylic acid having the following structural relationships as tothe position of the carboxylate groups and possessing the followingprescribed physical characteristics:) (a) a minimum molecular weight ofabout 350 calculated as to the acid form; (b) an equivalent weight ofabout 50 to about 80 calculated as to the acid form; (c) at least 45mole percent of the monomeric species having at least two carboxylradicals separated from each other by not more than two carbon atoms;(d) the site of attachment to the polymer chain or anycarboxylcontaining radical being separated by not more than 3 carbonatoms along the polymer chain from the site of attachment of the nextcarboxyl-containing radical. Specific examples are polymers of itaconicacid, aconitic acid, maleic acid, mesaconic acid, fumaric acid,methylene malonic acid, and citraconic aid and copolymers withthemselves and other compatible monomers such as ethylene), and (7)mixtures thereof.

Mixtures of organic and/or inorganic builders can be used and aregenerally desirable. Especially preferred are the mixtures of buildersdisclosed in the copending application of Burton H. Gedge, Ser. No.398,705, filed Sept. 23, 1964 and now US. Pat. 3,392,121, e.g., ternarymixtures of sodium tripolyphosphate, sodium nitrilotriacetate, andtrisodium ethane 1 hydroxy 1,1 diphosphonate.

These detergent compositions can optionally contain from about 1% toabout 50%, preferably about 1% to about 10%, by weight of an alcoholcontaining 1 to about 4 carbon atoms such as, for example, isopropanolor ethanol, to reduce the viscosity of the composition thereby causingit to be more readily pourable and also to reduce the tendency of thecomposition to become a gel.

These detergent compositions can also contain any of the usualadjuvants, diluents and additives, for example, perfumes,anti-tarnishing agents (e.g., sodium and potas sium silicates andbenzotriazole), anti-redeposition agents =(e.g., alkali metal andammonium salts of carboxymethyl cellulose), 'bacteriostatic agents, dyesor pigments (including optical brighteners), suds builders, sudsdepressors, and the like, without detracting from the advantageousproperties of the composition.

Normally the organic detergent components, the build ers, thephosphiniminophosphonium salt component, and the minor ingredients areincorporated into the composition prior to conversion into final productform, e.g., detergent granules, flakes, etc., but they can also be addedindividually in the form of particles or as liquids.

Turning now to processes for preparing the abovedescribedphosphiniminophosphonium salts, these salts can be prepared by any of anumber of processes but preferably are prepared according to one of twonovel processes described hereinafter. These novel processes can be usedto prepare not only the above phosphiniminophosphonium salts which areeffective and durable softening agents and effective emulsifying agents,but also other phosphiniminophosphonium salts known in the prior artwhich do not possess these advantageous softening and emulsifyingproperties but which are effective antibacterial agents. Accordingly,these processes are described hereinafter with sufiicient breadth tocover not only the preparation of the above novelphosphiniminophosphonium salts but also the preparation of these otherphosphiniminophosphonium salts which are known in the prior at and whichare effective antibacterial agents.

In one of these novel processes symmetrical phosphiniminophosphoniumsalts are prepared by heating an aminophosphonium salt having theformula 9 RlzRlsRllP Nfl wherein R is a radical selected from the groupconsisting of aliphatic radicals containing from 1 to 18 carbon atoms,phenyl and substituted phenyl; R and R are radicals selected from thegroup consisting of aliphatic radicals containing 1 to about 4 carbonatoms, phenyl and substituted phenyl; and Y is an anion selected fromthe group consisting of halides (such as chloride, bromide and iodide),cyanide, and azide. R R and R can each be of different chain lengthswithin the same compound. The aliphatic radicals in this formula can besaturated or unsaturated and branched or straight chain. For example,these aliphatic radicals can be alkyl, alkenyl, substituted alkyl, andsubstituted alkenyl radicals, the terms alkyl and alkenyl being definedas previously.

Suitable aminophosphonium salts are set forth in Table II below whereinR R R and Y are applied in the structural formula set forth above.

Dodecyl(tetrapropy1ene Dodecyl(stlsraight chain) p-Methylphenyl BenzylThe above aminophosphonium salts are heated in an inert atmosphere, forexample under vacuum, at a temperature ranging from about C. to about300 C. for a period ranging from about 0.5 hour to about 30 hours toprovide essentially complete reaction. Reaction temperatures rangingfrom about C. to 260 C. and reaction times ranging from about 1 hour toabout 20 hours are preferred.

It is preferred that no reaction solvent be employed 1n this processsince the use of a reaction solvent lowers the concentration ofaminophosphonium salt and can therefore necessitate longer reactiontimes. If no reaction solvent is employed a reaction temperature atleast 20 C. above the melting point of the aminophosphonium saltreactant is essential. If a reaction solvent is employed, such reactionsolvent must be inert with respect to the aminophosphonium salt and anyreaction product and is preferably a high boiling point aromatic oraliphatic hydrocarbon, such as, for example, dodecane.

The following equation represents a typical example of the reaction ofthis process:

The phosphiniminophosphonium product is separated from by-product by anyconventional separation technique, for example, by selectivelydissolving the product in a solvent, separating the dissolved productfrom undissolved by-product by filtration, and evaporating the filtrateto yield substantially pure product.

The aminophosphonium salt reactant of this process while not readilyavailable commercially, can be easily prepared. For example,aminophosphonium chlorides are conveniently prepared by reacting theappropriate trisubstituted phosphine in an inert atmosphere'and at roomtemperature with chloramine gas. The preparation of trisubstitutedphosphines is described in Hays, Ser. No. 461,669, filed June 7, 1965and now U.S. Pat. 3,389,183.

Turning now to the second of the two novel processes described hereinfor preparing phosphiniminophosphonium salts, this process can beemployed to prepare either symmetrical or unsymmetricalphosphiniminophosphonium salts. In this process an N-alkali-metalphosphinimine is reacted with a trisubstituted phosphine dihalide ordipseudohalide.

The N-alkali-metal phosphinimine for use herein is believed to be anovel compound. It has the structural formula wherein R is a radicalselected from the group consisting of aliphatic radicals containing from1 to about 18 carbon atoms, phenyl, and substituted phenyl; R and R areradicals selected from the group consisting of aliphatic radicalscontaining 1 to about 4 carbon atoms, phenyl, and substituted phenyl;and M is an alkali metal selected from the group consisting of sodium,potassium, and lithium. R R and R can each be of different chain lengthswithin the same compound and can be saturated or unsaturated andbranched or straight chain. For example, these aliphatic radicals can bealkyl, alkenyl, substituted alkyl, and substituted alkenyl radicals, theterms alkyl and alkenyl being defined as hereinbefore.

Suitable N-alkali-metal phosphinimines are set forth in Table III belowwherein R R R and M are applied in the structural formula set forthabove.

TABLE III X15 R50 R17 M Methyl Methyl Methyl Sodium. Ethyl EthyleneSameas abve.. Potassium Butyl Butyl l Octyl P Dodecyl (tetrapro- MethylMethyl Sodium.

py ne i Dodecyl(straight Same as above" Same as above Lithium.

chain Hexadecyl Ethyl do Potassium. Oleyl Methyl -do Lithium. IhenylPhenyl PhenyL. Same. Styryl Styryl Styry Do. oEthylphenyl o-EthylphenyL.o-EthylphenyL- Potassium. 3phenylpropyl 3-phenylpropyL. 3-phenylpropylSodium.

The trisubstituted phosphine dihalide or dipseudohalide for use hereinhas the structural formula R18R19R20PY21 wherein R is a radical selectedfrom the group consisting of aliphatic radicals containing from 1 toabout 18 carbon atoms, phenyl, and substituted phenyl; R and R areradicals selected from the group consisting of aliphatic radicalscontaining from 1 to about 4 carbon atoms, phenyl, and substitutedphenyl; and Y is selected from the group consisting of (1) halogens,such as chlorine, bromine, and iodine, and (2) pseudohalogens selectedfrom the group consisting of cyanide and azide, R R and R can each be ofdifferent chain lengths within the same compound and can be saturated orunsaturated and branched or straight chain. The term aliphatic isdefined as hereinbefore. Each Y can be different in the same compound.

The above N-alkali-metal phosphinimines are reacted with the abovetrisubstituted phosphine dihalides or dipseudohalides in an inertatmosphere, for example under argon, at a temperature ranging from about0 C. to about 50 C. for a period ranging from about 0.5 hour to about 30hours to provide essentially complete re action. Room temperature is apreferred reaction temperature. Reaction times ranging from about 1 hourto about 20 hours are preferred.

A reaction solvent is employed in this process which is compatible withthe above reactants and with the reaction product. This reaction solventis preferably an aliphatic or aromatic hydrocarbon such as benzene,hexane, dodecane, and the like.

The following equation represents a typical example of the reaction ofthis process:

16 hours (0 119) 3P=NLi O12H25(CH3) zPClg room temperature Thephosphiniminophosphonium salt product is easily separated fromby-product since ordinarily the product is dissolved in the reactionsolvent while the by-product is not. For example, the product can beisolated by decanting the solvent phase and evaporating this phase toyield substantially pure product.

The reactants in this process are not readily available commercially butcan be prepared by a number of methods. For example, N-alkali-metalphosphinimines can be prepared by reacting an aminophosphonium halide orpseudohalide, e.g., chloride, the preparation of which is describedhereinbefore, with aliphatic hydrocarbon alkali-metal salt. Twoequivalents of aliphatic hydrocarbon alkali-metal, R M, are employed foreach equivalent of aminophosphonium halide or pseudohalide,

In these structural formulae R R R and M are defined as previously; R isan aliphatic radical containing from 1 to about 12 carbon atoms, theterm aliphatic being defined as previously; and Y is selected from thegroup consisting of chloride, bromide, iodide, azide, and cyanide. Thereaction is conveniently carried out without external heating at atemperature ranging from about 10 C. to about C. in an inert atmosphere,such as argon, with a reaction time ranging from about 0.5 hour to about10 hours or more. The following equation represents a typical example ofthe preparation of an N-alkalimetal phosphinimine:

3 hours 9)3 2041110 LiCl The trisubstituted dihalide or dipseudohalidecan be conveniently prepared, for example, by reacting trisubstitutedphosphines with a halogen or pseudo'halogen. This reaction is carriedout with no external heating, for example in a solvent such as benzeneand in an inert atmosphere such as argon. Reaction is substantiallycomplete within about 10 minutes. As previously mentioned, thepreparation of trisubstituted phosphines is described in Hays, Ser. No.461,669, filed June 7, 1965 and now U.S. Pat. 3,389,183.

It is noted that the reactants in the above two novel processes for theproduction of phophiniminophosphonium salts contain as anion-producingconstituents only halogens and the pseudohalogens, azide and cyanide.This limitation in the structure of the reactants is essential for theproduction of high yields of phosphiniminophosphonium salt sincereactants containing oxygencontaining anion-producing constituents forexample produce high yields of by-products. Thus, these two novelprocesses are advantageously used directly only to producephosphiniminophosphonium halides, azides and cyanides. However, theanions in the phosphiniminophosphonium salt products produced by thesenovel processes can be converted to other anions by means ofconventional techniques, for example, by means of an ion exchangecolumn. 1

All percentages and parts herein are by weight unless otherwisespecified. All aliphatic radicals herein are straight chain unlessotherwise specified. In all reactions herein where such reaction iscarried out under an inert atmosphere, any inert atmosphere can beemployed; for

I 1 example, these reactions can be carried out in a vacuum or underinert gases such as argon, nitrogen or helium. The following examplesare illustrative of the present invention and are not to be construed inany way as limiting the scope of the invention.

EXAMPLE I Preparation ofdimethyldodecylphosphiniminodimethyldodecylphosphonium chloride 6aC12H25( C a)2 N I C s)2 12 Dimethyldodecylaminophosphonium chloride,

C12I'{25(CI I3)2PGa NI'I2C1e was prepared as follows: A 500-ml.three-necked roundbottomed flask was fitted with a gas inlet tube, apaddle stirrer driven by an electric motor, and a gas outlet tubeconnected to a mineral oil bubbler. Twelve grams ofdimethyldodecylphosphine prepared according to the method of Hays, Ser.No. 461,669, filed June 7, 1965, and now US. Pat. 3,389,183, was addedto the flask which previously had been evacuated and filled with argon.Then 300 ml. of dry benzene was added. The gas 25 inlet tube wasarranged so as to extend below the surface of the benzene and then wasconnected to a chloramine gas generator. Two equivalents of chloraminegas were then passed into the phosphine solution causing heat evolutionand a white precipitate to form. The mixture was stirred under argon forone hour without external heating to ensure complete reaction. The whitesolid in the resulting solid-solution mixture was separated from thesolution by filtering. The white solid was then extracted twice with 300ml. portion of acetonitrile at 82 C., and the remaining white solid,primarily consisting of ammonium chloride, was discarded. Theacetonitrile was evaporated from the combined extracts to yield a whitesolid. Recrystallization of this white solid from 300 ml. ofacetonitrile yielded 12 grams of substantially puredimethyldodecylaminophosphonium chloride.

In a heavy-walled glass pyrolysis tube was placed 2.622 grams (9.3mmoles) of the above prepared dimethyldodecylaminophosphonium chloride.The tube with its contents was then evacuated to 0.1 mm. Hg, sealed atthis pressure, and placed in an oil bath that had been preheated to 195C. Heating was maintained at this temperature for 16 hours. Aftercooling to room temperature, the tube was opened to the air and thecrystalline mass partially dissolved in ml. of benzene at 80 C. Theinsoluble solid was removed by filtration and shown to be ammoniumchloride by infrared analysis. The benzene filtrate was evaporated invacuo to yield a white solid which was recrystallized from 40 ml. of /50volume benzene-hexane mixture to yield 1.352 grams ofdimethyldodecylphosphiniminodimethyldodecylphosphonium chloride EXAMPLEII Preparation ofdimethyltetradecylphosphiniminodimethyltetradecylphosphonium chloride tobe ammonium chloride by infrared analysis. The filtrate was evaporatedto give a white solid which was recrystallized from acetonitrile toyield 1.46 grams of substantially puredimethyltetradecylphosphiniminodimethyltetradecylphosphonium chloride.

EXAMPLE III Preparation ofdimethylhexadecylphosphiniminodimethylhexadecylphosphonium chloride In aheavy-walled glass pyrolysis tube was placed 5.150 grams (15.25 mmoles)of dimethylhexadecylaminophosphonium chloride, C H (CH P NH Clsynthesized in a manner similar to the dimethyldodecylaminophosphoniumchloride of Example I. The tube with its contents was then evacuated to0.1 mm. Hg, sealed at this pressure, and placed in an oil bath that hadbeen preheated to 200 C. Heating was continued at this temperature for16 hours. After cooling to room temperature the crystalline mass waspartially dissolved in ml. of acetonitrile at 82 C. The insoluble solidwas removed by filtration and was shown to be ammonium chloride byinfrared analysis. The filtrate was cooled to deposit white crystalswhich were recrystallized from acetonitrile to yield 2.96 grams ofsubstantially puredimethylhexadecylphosphiniminodimethylhexadecylphosphonium chloride.

EXAMPLE IV Preparation of triphenylphosphiniminotriphenylphosphoniumchloride GB @PmNaP (in In a heavy-walled glass pyrolysis tube was placed10.29 grams (32.8 mmoles) of triphenylaminophosphonium chloride, PNH Clsynthesized in a manner similar to the dimethyldodecylaminophosphoniumchloride of EX- ample I. The tube with its contents was then evacuatedto 0.1 mm. Hg, sealed at this pressure, and placed in an oil bath thathad been preheated to 255 C. Heating was maintained at this temperaturefor 20 hours during which time the contents of the tube turned black.After cooling to room temperature, the entire crystalline mass whichresulted was dissolved in 150 ml. of water at 0, treated with charcoalto remove color and filtered to separate the resulting colorlesssolution and the charcoal. The colorless filtrate was cooled to depositwhite crystals. The crystals were separated from the remaining solutionby decanting. The crystals were allowed to dry to provide 7.80 grams ofsubstantially pure triphenylphosphiniminotriphenylphosphonium chloride.

Other symmetrical phosphiniminophosphonium salts are prepared if molarequivalents of other aminophosphonium salts are substituted for theaminophosphonium salts in the above examples. For example,trimethylphosphiniminotrimethylphosphonium bromide is prepared iftrimethylaminophosphonium bromide is substituted for thedimethyldodecylaminophosphonium chloride of Example I;dibutylundecylphosphiniminodibutylundecylphosphonium iodide is preparedif dibutylundecylaminophosphonium iodide is substituted for thedimethyltetradecylaminophosphonium chloride of Example II;dimethyloleylphosphiniminodimethyloleylphosphonium azide is prepared ifdimethyloleylaminophosphonium azide is substituted for thedimethylhexadecylaminophosphonium chloride in Example III; and dimethylp methylphenylphosphiniminodimethyl-p-methylphenylphosphonium cyanide isprepared if dimethyl p methylphenylaminophosphonium cyanide issubstituted for the triphenylaminophosphonium chloride of Example IV.

The triphenylphosphiniminotriphenylphosphonium chloride prepared inExample IV and the trimethylphosphin- 13 iminotrimethylphosphoniumbromide and dimethyl p methylphenylphosphiniminoimethyl pmethylphenylphosphonium cyanide prepared above are efiectiveantibacterial agents.

EXAMPLE V Preparation ofdimethyldodecylphosphiniminotri'butylphosphonium chlorideN-lithiotributylphosphinimine, (n-C H P=NLi, was prepared as follows: Ina 100 ml. one-necked roundbottom flask was placed 11.57 grams (45.7mmoles) of tri-n-butylaminophosphonium chloride, (n-C H P+ N I-I Cl9,and 30 ml. of benzee under an atmosphere of argon. A solution oftri-n-butylaminophosphonium chloride in benzene was then formed by meansof vigorous stirring with a magnetic stirrer. To this solution at roomtemperature was added 57.4 ml. of 1.59 normal solution of n-butyllithium-hexane solution (91.2 mmoles of n-butyl lithium or about 2equivalents), and vigorous heat and gas evolution occurred. Theresulting yellow solution was stirred for three hours under argonwithout addition of external heat. The resulting solution containingN-lithiotributylphosphinimine was used hereinafter without isolation orpurification of the formed intermediate. The abovetri-n-butylamiuophosphonium chloride was synthesized in a manner similarto the dimethyldodecylaminophosphonium chloride of Example I.

Dimethyldodecylphosphine dichloride was then prepared as follows: In aone-necked 100 ml. round-bottomed flask equipped with a rubber cap andfilled with argon was placed 7.05 grams (30.7 mmoles) ofdimethyldodecylphosphine, and 50 ml. of dry benzene. The formed solutionwas vigorously stirred while 772 ml. of chlorine gas was injected intothe cappedflask. The reaction mixture was then stirred for one hour atroom temperature. The resulting solution containingdimethyldodecylphosphine dichloride was used hereinafter withoutisolation or purification of the formed intermediate. The abovedimethyldodecylphosphine was prepared by the method of Hays, previouslyreferred to.

At this point the above-formed N-lithiotributylphosimine solution wasadded to the above-formed dimethyldodecylph'osphine dichloride solution.This addition was stirred for 16 hours with no external heating toprovide an insoluble white SOlLld and a clear supernatant. The clearsupernatant was decanted to separate it from the solid. Evaporation ofsolvent from the supernatant liquid gave a yellow oil. This oil wasdissolved in 50 ml. of carbon tetrachloride at 76 C. After cooling toC., a white solid was deposited. Recrystallization of this solid fromcarbon tetrachloride yielded 14.58 grams ofdimethyldodecylphosphiniminotributylphosphonium chloride.

Other phosphiniminophosphonium salts are prepared by the method of thisexample if molar equivalents of other N-alkali-metal phosphinimines aresubstituted for the N-lithiophosphinimine above and/ or molarequivalents monoiodidemonocyanide to form a mixture of dimethylpethylphenylphosphiniminiobutylphosphonium iodide and cyanide. 1

vThehalide and pseudohalide anions of the phosphiniminophosphonium saltsformed in Examples I-V above can be converted to other anions byconventional ion exchange techniques. For example, thedimethyldodecylphosphiniminotributylphosphonium chloride formed abovecan be converted to dimethyldodecylphosphiniminotributylphosphoniumnitrate in this manner.

EXAMPLE VI Emulsions of carbon tetrachloride One-fourth gram ofdimethyldodecylphosphiniminotributylphosphonium chloride prepared inExample V was mixed with 4 ml. of carbon tetrachloride. This mixture wasmixed with 4 ml. of water to provide a carbon tetrachloride/Wateremulsion which is stable for more than twelve hours.

Substantially equal emulsification results were obtained when thephosphiniminophosphonium salts prepared in Examples I, II and III weresubstituted for the dimethyldodecylphosphiniminotributylphosphoniumchloride above. Astable emulsion was not formed when the triphenylphosphiniminotriphenylphosphonium chloride prepared in Example IV wassubstituted for the dimethyldode'cylphosphiniminotributylphosphoniumchloride above.

The above carbon tetrachloride/water emulsions are useful in'the drycleaning of textiles and as broad spectrum solvents suitable forcleaning articles soiled with both oil-soluble and water-soluble soils.

EXAMPLE VII Tetrachloroethylene emulsions A composition containing thenew phosphiniminophosphonium salts suitable for use in the dry cleaningof textiles contains:

Percent Dimethyldodecylphosphiniminotributylphosphonium chloride 2.0Water 0.5 Tetrachloroethylene 97.5

For application to textiles this composition can be diluted to containas much as 50% water. After being mixed, this diluted composition is anemulsion which is stable for at least 1 hour, and as such is suitablefor application to textiles for dry cleaning purposes.

Other new phosphiniminophosphonium salts, for exarnple, thecompoundsprepared in Examples I, II, and III can replace thedimethyldodecylphosphiniminotributylphosphonium chloride in the aboveexample to provide stable emulsions upon dilution of the composition.

Ordinarily, useful dry cleaning compositions consist essentially of fromabout 0.5% to about 5% phosphiniminophosphonium salt, from about 0.5% toabout 50% water and from about 45% to about 99% tetrachloroethylene.

The following two examples illustrate textile softener compositionscontaining the new phosphiniminophosphonium salts. These compositionsare applied to textiles as water solutions containing 50 ppm.phosphiniminophosphonium salt. When so applied'these compositionsprovide effective and durable softening. The scftening effect remainseven after five washings of the treated textile.

EXAMPLE VHI A suitable liquid textile softener composition contains:

Percent Dimethylhexadecylphosphiniminodimethylhexadecylphosphoniumchloride 5 Isopropanol 2 3,4,4-trichlorocarbanilide 1 The condensationproduct of 9 moles of ethylene oxide with 1 mole of nonylphenol 1 Color0.003 Perfume 0.25

Water balance 1 5 EXAMPLE 1x A suitable granular textile softenercomposition contains:

Percent Urea 75Dimethylhexadecylphosphiniminodimethylhexadecylphosphonium chloride 25EXAMPLE X In the manufacture of sheeting, 80 x 80 cotton sheeting ispassed through a pad containing a water solution ofdimethyloctadecylphosphiniminodimethyloctadecylphosphonium chloride. Thewater solution contains 75 p.p.m. of the phosphiniminophosphonium salt.The sheeting is effectively softened and retains this softened effecteven after the consumer has washed it five times with no application oftextile softener.

Other new phosphinimidophosphonium salts, e.g., the compounds preparedin Examples I, II, III and V, can be used in this example in place ofthe dimethyloctadecyl salt with similar results.

The following Examples XI-XVII illustrate heavy-duty laundry detergentcompositions which contain as a softening agent the newphosphiniminophosphonium salts of this invention. These detergentcompositions can be used to clean and soften textiles such as sheets andtowels.

EXAMPLE XI Percent Dimethyldodecylphosphiniminotributylphosphoniumchloride 3 Tallow alcohol ethoxylated with moles of ethylene oxide permole of alcohol Sodium tripolyphosphate 50 Sodium sulfate 32 EXAMPLE XIIPercent Dimethyloctadecylphosphiniminotrimethylphosphonium sulfate 7Coconut alcohol (2%C 66%C 23 %C 9%- C ethoxylated with 6 moles ofethylene oxide 16 EXAMPLE XV PercentDimethylhexadecylphosphiniminotrimethylphosphonium borate 15Dimethyldodecylamine oxide 15 Tetrapotassium pyrophosphate 30 Sodiumtoluene sulfonate 8 Ethanol 10 Water 29 EXAMPLE XVI PercentDimethyltetradecylphosphiniminodimethyltetradecylphosphonium acetate 5Dimethyldodecylphosphine oxide 15 Sodium tripolyphosphate 60 Sodiumsulfate 20 EXAMPLE XVII PercentDiethylpentadecylphosphiniminotrimethylphosphoniurn iodide 5Dimethylcoconut (2%C 66%-C 23 %C 9%C alkylammonio hydroxypropanesulfonate- 20 Trisodium ethylidene diphosphonate 30 Sodium sulfate 45The following Examples XVIII and XIX illustrate light-duty liquiddetergent compositions containing as a softening agent the newphosphiniminophosphonium salts of this invention. These detergentcompositions are suitable for cleaning and softening delicate clothingsuch as sweaters or underwear.

EXAMPLE XVIII PercentDimethylhexadecylphosphiniminodimethylhexadecylphosphonium chloride 10Component A, described below 35 Ethanol 10 Water 45 EXAMPLE XIX PercentDimethyldodecylphosphiniminodimethyldodecylphosphonium chloride 10Component A, described below 32 Ethanol 10 Water 48 In the aboveexamples component A is a tertiary amine oxide having a long alkyl chainderived from middle cut coconut alcohol (containing 2%Cm, 66%C 23 %C and9%C and two methyl groups.

Other phosphiniminophosphonium salts can be substituted for thephosphiniminophosphonium salts of Examples XI-XIX to provide laundrydetergents. For example,

dimethyltetradecylphosphiniminodimethyltetradecylphosphonium chloridecan be substituted for the dimethyldodecylphosphiniminodimethyl- Idodecylphosphonium chloride of Example XIX to provide a light-dutyliquid detergent having softening properties. Moreover, various otherdetergent actives can be substituted for the detergent actives inExamples XI-XIX above. For example, various ampholytic detergents, e.g.,dodecyl-beta-alanine, the sodium salt of N-dodecyl taurine, or disodiumN- dodecyl aspartate, can replace component A in Examples XVIII and XIXabove to provide light-duty liquid detergents, having softeningproperties.

The previously described novel phosphiniminophosphonium salts also haveutility as antibacterial agents, wetting agents, detergents,solubilizing agents, waterproofing agents, and gelling or thickeningagents. These salts also are very soluble and thus are veryadvantageously used in various compositions such as softenercompositions and detergent compositions; this is because they remain insolution even though the composition containing them freezes and laterthaws. On the other hand, conventional softening additives which aresuspended in such compositions tend to separate from the rest of thecomposition under these same freezing-thawing circumstances.

IEXAMPLE xx' N-lithiodimethyldodecylphosphinimine was prepared byreacting dimethyldodecylaminophosphonium chloride with n-butyl lithiumaccording to the method for preparing N-lithiotributylphosphinimine inExample V. This prepared compound is a reactive intermediate and can beused It the preparation of the novel phosphiniminophosphonium salts ofthis invention according to the second of the two novel processesdescribed herein. For example, this N-lithiodimethyldodecylphosphiniminecan be reacted with tributylphosphine dichloride to producedimethyldodecylphosphiniminotributylphosphonium chloride.

I claim:

1. A liquid textile softener composition consisting essentially byweight of from about 1% to about 15% of a phosphiniminophosphonium salthaving the structural formula wherein R is alkyl of from 1 to about 18carbon atoms; R R R and R are each alkyl of from 1 to about 4 carbonatoms; R is alkyl of from about 12 to about 18 carbon atoms; and X is ananion which permits solubility and hydrolytic stability of the salt; andfrom about 85% an mp n r 11 11 11 wherein R is alkyl of from 1 to about18 carbon atoms; R R R and R are each alkyl of from 1 to about 4 carbonatoms; R is alkyl of from about 12 to about 18 carbon atoms; and X is ananion which permits solubility and hydrolytic stability of the salt; andfrom about 50% to about 95% urea.

5. The method of softening textiles by the application of a watersolution of a phosphiniminophosphonium salt having the structuralformula wherein R is alkyl of from 1 to about 18 carbon atoms; R R, Rand R are each alkyl of from 1 to about 4 carbon atoms; R is alkyl offrom about 12 to about 18 carbon atoms; and X is an anion which permitssolubility and hydrolytic stability of the salt; said solutioncontaining from about p.p.m. to about 500 p.p.m. of said salt.

6. The method of claim 5 wherein the concentration 1 8 ofphosphiniminophosphonium salt in said solution ranges from about 25p.p.m. to about 100 p.p.m.

7. A softener and detergent composition consisting essentially of byweight:

(I) from about 1% to about 15 of a phosphiniminophosphonium salt havingthe structural formula PR R R wherein R is alkyl of from 1 to about 18carbon atoms; R R R and R are each alkyl of from 1 to about 4 carbonatoms; R is alkyl of from about 12 to about 18 carbon atoms; and X is ananion which permits solubility and hydrolytic stability of the salt;

(II) from about 5% to about 95% of a compatible detergent selected fromthe group consisting of nonionic, Zwitterionic, and ampholytic syntheticdetergents; and

(III) from about 0% to about water-soluble alkaline detergency buildersalt.

8. The softener and deteryent composition of claim 7 wherein the amountof water-soluble alkaline detergency builder salt present is from about10% to about 90% by weight of the composition.

9. The softener and detergent composition of claim 8 wherein an alcoholcontaining from 1 to about 4 carbon atoms is present in an amount offrom about 1% to about 5 0% by weight of the composition.

10. The softener and detergent composition of claim 9 wherein thealcohol is present in an amount of from about 1% to about 10%.

11. The softener and detergent composition of claim 9 consistingessentially of:

(I) from about 1% to about 15% of the phosphiniminophosphonium salt ofclaim 9; (II) from about 5% to about of a compatible detergent selectedfrom the group consisting of (1) nonionic synthetic detergents selectedfrom the group consisting of:

(a) alkyl phenol polyethylene oxide condensates wherein the alkylradical contains from about 6 to about 12 carbon atoms and containingfrom about 5 to about 25 moles of ethylene oxide per mole of phenol,

(b) compounds containing from about 40% to about 80% polyoxyethylene byweight and having a molecular weight of from about 5000 to about 11,000,resulting from the reaction of ethylene oxide with a hydrophobic baseconstituted of the reaction product of ethylene diamine and excesspropylene oxide, said base having a molecular weight of from about*2500to about 3000,

(c) the condensation product of aliphatic alcohols having 8 to about 18carbon atoms with from about 10 to about 30 moles of ethylene oxide permole of alcohol,

((1) trialkyl amine oxides wherein one alkyl radical contains from about10 to about 18 carbon atoms, from 0 to about 5 ether linkages, and from0 to about 2 hydroxy groups, and wherein the other two alkyl radicalseach contains from 1 to about 3 carbon atoms, from 0 to about 2 etherlinkages, and from 0 to about 2 hydroxy groups,

(e) trialkyl phosphine oxides wherein one alkyl radical contains from 10to 18 carbon atoms, from 0 to about 5 ether linkages, and from 0 toabout 2 hydroxy groups, and wherein the other two alkyl radicals eachcontain from 1 to about 3 carbon atoms, from 0 to about 2 etherlinkages, and from 0 to about 2 hydroxy groups,

(f) dialkyl sulfoxides having the formula wherein R is an alkyl radicalcontaining from about 10 to about 20 carbon atoms, from about to aboutether linkages, and from about 0 to about 3 hydroxyl groups, there beingat least one moiety of R which constitutes a carbon chain containing noether linkages and containing from to 18 carbon atoms, and wherein R isa short alkyl chain containing from about 1 to about 3 carbon atomshaving 02 hydroxyl groups attached to said short alkyl chain; (2)zwitterionic detergents having the formula wherein R is an alkyl radicalcontaining from about 10 to about 18 carbon atoms and from about 9 toabout 5 ether linkages, wherein R and R are each selected from the groupconsisting of alkyl groups containing from 1 to about 3 carbon atoms andhydroxy alkyl groups containing from 1 to about 3 carbon atoms, whereinR is selected from the group consisting of alkylene and hydroxysubstituted alkylene groups containing from 1 to about 4 carbon atoms,and wherein Z is selected from the group consisting of 0 II II C0 and-ISIO groups (3) amphoteric detergents selected from the groupconsisting of:

(a) alkyl-beta-alanines, (b) N-alkyl taurines, (c) N-alkyl aspartates,and (d) mixtures thereof wherein the alkyl groups contain from about 8to about 18 carbon atoms, and (4) mixtures thereof;

20 (III) from about 10% to about 90% of builder salts selected from thegroup consisting of:

(1) inorganic salts selected from the group consisting of sodium andpotassium (a) tetraborates, (b) bicarbonates, (c) carbonates, (d)tripolyphosphates, (e) pyrophosphates, (f) orthophosphates, (g)hexametaphosphates, and (h) mixtures thereof;

(2) organic salts selected from the group consisting of sodium andpotassium (a) ethylenediaminetetraacetates, (b) nitrilo triacetates, (c)N (2 hydroxyethyl)-nitrilo diacetates, (d) phytates, (e)ethane-1-hydroxy-1,1-diphosphonates, (f) isopropylidine diphosphonates,(g) benzyl methylidene diphosphonates, (h) halomethylidenediphosphonates, (i) mixtures thereof;

(3) polycarboxylate builder materials comprising water-solub1e salts ofpolymeric aliphatic polycarboxylic acids having the following structuralrelationships as to the position of the carboxylate groups andpossessing the following prescribed physical characteristics: (a) aminimum molecular weight of 350 calculated as to acid form; (b) anequivalent weight of about 50 to about 80 calculated as to acid form;(0) at least 45 mole percent of the monomeric species having at leasttwo carboxyl radicals separated from each other by not more than twocarbon atoms; and (d) the site of attachment to the polymer chain ofcarboxyl-containing radical being separated by not more than threecarbon atoms along the polymer chain from the site of attachment of thenext carboxyl-containing radical being separated by not more than threecarbon atoms along the polymer chain from the site of attachment of thenext carboxyl-containing radical.

References Cited UNITED STATES PATENTS LEON D. ROSDOL, Primary ExaminerP. E. WILLIS, Assistant Examiner U.S. Cl. X.R.

233 3 UNITE STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,553,129 Dated January 5', 1971 Inventor(s) Terrence William Rave It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

[- Column 6, lines 64 and 65, (e.g. sodium and phytates see U.S Pat.2,739,942) should read (e.g. sodium and potassium phytates See U.S. Pat.2,739,942)

Column 9, line 49, formuls R R R PY should read R R R 'PY Column 13,lines 46 and 47 "This addition was stirred f1 16 hours with no externalheating should read This addit was effected with all compounds underargon. The mixture wa stirred for 16 hours with no external heatingColumn 13, line 69, "tributyllphosphinemonoiodidemonocyanide" shouldread tributylphosphinemonoiodidemonocyanide Column 15, line 53,"Dimethyloctadecylphosphiniminotrimethylphosphonium sulfate" should readDibutyloctadecy phosphiniminodimethyloleylphosphonium nitrate Column 16,line 3, under the heading "Percent" the figu: "15" should read 8 Column17, line 16, "used n" should read used in Column 18, line 23,"deteryent" should read detergen1 Signed and sealed this 8th day of June1971 (SEAL) Attest: L EDWARD M.FLE1GHER,JR. WILLIAM E. SCHUYLER, JE

Attasting Officer 1 Commissioner of Patent:

